N-myristyl-3-hydroxybutylamines and their salts



N-MYRISTYL-S-HYDROXYBUTYLAMINES AND THEIR SALTS Frank J. 50. Cranford, N. J.

No Drawing. Application April 3, 1956 Serial No. 575,715

'10 Claims. (Cl. 260-501) v This invention relates to a new class of chemical compounds, namely, the N-myristyl-B-hydroxybutylamines and their salts. This application is a continuation-in.- part of copending application Serial No. 300,331, filed July 22,'1952, now abandoned.

Many amines and quaternary ammonium compounds are known and certain of these compounds have been foundto possess bactericidal or fungicidal properties particularly when there is a long chain alkyl group attached to the nitrogen of the amine. Thus, Shelton et al. (J. A. C. 8., vol. 68, pp. 753 to 759; May 1946) tested a large number of such compounds and concluded that the activity of such series reaches a peak when the cetyl group is present. They further concluded that the presence of hydroxyl groups tends to diminish the germicidal activity of the compounds tested.

As pointed out in said copending applicatioryl have discovered that myristyl amines differ from other amines and amine 'salts in that their bactericidal and fungicidal activity is enhanced, provided the amine'contains an alkanol group. Thus, for example, N-myristyl diethanolamine hydrochloride possesses bactericidal and fungicidal activities which are from 10 to 100 t imes as great as those of the corresponding octyl,'undeceny1, lauryl, cetyl and stearyl compounds.

I have further discovered that the bactericidal and fungicidal activity even among the N-myristyl alkanolamines and their salts varies greatly, depending upon the nature of the alkanol group present in the compound. Thus, the N myristy1-3-hydroxybutylamines and their salts possess surprisingly greater bactericidal and fungicidal properties than those N-myristyl amines containing other 'alkanol groups such as ethanol or isopropanol groups, for example.

Accordingly," the present inventlon is directed to .N-.

myristyl-3-hydroxybutylamines and their salts ."Thes e compounds are not only useful as bactericidal and fungicidal agents, but further are useful as rodent repellents and may be used as detergents and emulsifying agents,

and for other purposes. 1

Compounds of the class to which this invention relates are the amines and salts of the amines having the composition indicated by the general formula radical an he. y roxy di al in. the .hutanol group. is 7.

attached to the carbon atom third removed from the it n t e amine. .1...

When Ris hydrogemthefollowing three amines are possible: N-myris tyl-3-hydroxy-butylamine "CHEM OH:

\ l /N-CH2CH7OHOH 2,874,185 Patented Feb. 17, 1 5

- 2 N-myristyl-3-hydroxy-2-methyl propylamine CnHao CH:

N- CHaCHCH OH H N-myristyl-3-hydroxy-l-methyl' propylamine Cu a: CH1

-CHCH:CH1OH The salts ofthe foregoing amines may be represented by the formula .lauryl and their isomers and their monohydroxy derivatives. In the alternative, R may, of course, be hydrogen.

The principal object of the present invention is to provide a new class of compounds consisting of the secondary and tertiary amines which contain a myristyl radical attached to the nitrogen of the amino group and a butanol group which has a hydroxyl attached to the carbon atom third removed from the-amino group, to-

gether'with the salts of such amines.

These and other objects and features of the present invention will appear from the following description thereof in which reference is made to particular compounds and methods of producing the same for the purpose of indicating the nature of the present invention and some of its particular applications, but without intending to limit the scope of the invention thereto.

The compounds of the present invention are secondary or tertiary amines as defined above and are herein referred to as N-myristyl-3-hydroxybutylamines," where as the compounds wherein the remainingvalences of the nitrogen are satisfied by hydrogen and an anion are referred to herein as salts.

When the compounds are salts, substantially any anion may be present such as a halide, sulfate, monoethyl sulfate, phosphate, acetate, propionate, lactate, citrate, undecylenate, tartrate, salicylate, phenate, chlorophenate, chlorophenoxyacetate, thymate and chlorothymate, for example.

In order to illustrate typical compounds of the class to which the invention relates and indicate methods in which they may be produced, the following examples are cited:

EXAMPLE I.-MYRISTYL- B-HYDROXYBUTYL AMINE M01. Grams Moles Wt. Used Myristyl Bromide 277.2 277.2 1.0 4-amino-2-butano1 89.1 187.1 2.1

.with water, treated with caustic soda solution, washed again three times with water and then separated. Benzene was then added to remove the water. After the benzene was distilled off atatmospheric pressure, the compound was distilled under reduced pressure.

B. pt.=l86-206 C. (3 mm.) mostly at 186488 C.

(3 mm.) M. pt.=58-62 c.

It is believed to have the following structural formula CHzCHzCHOH Cu ae-N EXAMPLE II N-myristyl-3- ydroxy-secondary butylamine (N-myristyl-3-hydroxy-1-methylpropylamine) may be prepared by the method described under Example I by the reaction of the myristyl chloride, bromide or iodide with 3- hydroxy-secondary butylamine or as follows:

Eight hundred fifty-two (852) grams (4 moles) of myristyl amine was weighed in a two liter three necked flask equipped with a mechanical stirrer and a dropping funnel. The myristyl amine was warmed to 90 and then 3-chlorobutanol-1 was added dropwise while stirring and maintaining the temperature between 90l00 C. throughout the addition. The addition was stopped when 217 g. (2 moles) of 3-chlorobutanol-1 had been added. The contents were maintained, while stirring, at 100 C. for two hours more.

The composition was thoroughly washed three times with 350 cc. of a caustic soda solution and then three times with 400 cc. portion of water. The composition was dried by the addition of 500 cc. of benzene and distilling the benzene-water azeotrope at atmospheric pressure. The contents were fractionated at a reduced pressure of one millimeter of mercury. After recovering the myristyl amine, the N-myristyl-3-hydroxyl-methylpropylamine was distilled and the fraction boiling 145158 C. (1 mm.) was collected. Practically all boiled at 152 C. (1 mm.) and had a melting point of around 5859 C. It is believed to have the following structural formula H Other typical amines of the class to which this invention relates are as follows:

EXAMPLE III.N-MYRISTYL-3-HYDROXY- 2-METHYLPROPYLAMINE CiiHan Salts of these and other amines may be prepared in the usual way by contacting the amine, preferably in a solvent with a molar equivalent quantity of an acidic compound or a lower molar equivalent amount of the acidic substance if desired in the event that the acidic substance has more than one replaceable acid hydrogen.

Other typical salts of the present invention which have been prepared are the following:

EXAMPLE VI.MYRIS'IYL 3-HYDROXYBUTYL AMMONIUM CHLORIDE M01. Grams Moles Wt. Used N-myristyl-B-hydroxybutyl amine 285.3 45.0 0.16 Hydrogen Chloride 36.5 5.5 0.15

The amine was dissolved in 54 grams of benzene in a flask equipped with a mechanical stirrer and inlet tube. Dry HCl was allowed to bubble into the reaction flask for five minutes, at the end of which time 7.5 grams of HCl was absorbed. The reaction mixture turned pink at this point. On cooling, crystals formed, these were filtered and recrystallized twice. The final product was white in color and is believed to have the following structural formula CuHza CHnOHzCHOHOHa EXAMPLE IX.N-MYRISTYL- 3-HYDROXYBUTYL AMMONIUM PROPIONATE CuHzn OHACHQCHOHOH;

H H CHaCHzCOO' The influence of the myristyl group as compared with other long chain alkyl groups, in increasing the bacteri- C H OH I cidal and fungicidal activity of alkyl alkanol amlnes and N-CH;CHzOHCH their salts is made evident by the following results ob- CHH tamed 111 carrying out tests under identical conditions.

Table I Compound S. aureua B. typhoaus Interdigitale T. rubrum Deeyl 3-hydroxy butyl ammonium chloride. no action 1 to no action 1 to no action 1 to no action 1 to 1,000. 1,000. ,000. 1,000. effective 1 to effective 1 to do Do. Lauryl 3-hydroxy butyl ammonium 1,000. 1,000.

chloride. not 1 to 5,000.. not 1 to 5,000- Myrlstyl 3-hydroxy butyl ammonium effective 1 to effective 1 to efiectlve 1 to efiective 1 to chloride. 10,000. 10,000. 5,000. 5,000.

The same influence is indicated by the following tests:

thousand parts of soap is sufficient show activity. Greater or lesser amounts may be used if desired depend Table ll mg upon the activity required and in this case, the free compound s- Lmm B Whom amine 1s preferredbut not required where the soap is a 5 salt of a fatty acid. Decyl 3-hydroxy-1-methylpropyl amno action 1 to no action 1 to It also fomid that i compound? .have .mdent M gg gr 1 th 1 1 ii ,(m repellent properties when incorporated in food, rope,

yr y y oxy- -me ypropy 0 active 1 t0 efiective 1 to ammonium cmmde I 0. 5,000 twine, textiles, paper, plastics, seeds, wood, etc., and as Cetyl 3-hydroxy-1- ethylpropyl am? effective 1 to eflective 1 t0 'b 0 rodent t k When applied to the surface, 111011111111 chloride- 1 g 1 either alone or in suitable coating compositions, of box Stearyl3-hyd1oxy-1-methy1propylam- 5 n t e'fiective 1 board, paper surfaces, plastic coatings for electrical wire 1110mm chlorldeto 1,000 lnsulation, etc. For example, 0.5% by weight of N- myr1styl-3-hydroxy-l-methyl propylamine has a rodent re- An even more striklng increase 111 the bacterrcldal and pellency index K of 97.0 'as defined by Dr. James B. fungicidal activity is eifected by reason of the presence of De Witt, Patuxent Research Refuge, U. S. Department of the S-hydroxy butyl radical as compared with its homo- Interior. logues as evidenced by the results of tests set forth in the Although typical compounds of the class consisting of following table. the N-myristyl-3-hydroxybutyl amines and their salts have Table III Compound S. aureus B. iyphosus Interdigitale T. rubmm Myristyl z-hydroxy butyl amine efiective 1 to effective 1 to 1 to 5,000 1 to 5,000.

10,000. 10,000. reflective 1 to effective 1 to not effective 1 effective 1 to Myristyl di-iso-propauol amine 1,000. 1,000. to 1,000. 1,000.

not 1 to 5,000-. not 1 to 6,000-. not 1 to 5,000. nott eliiggtive 1 eflfggge 1 to efiletgrze 1 t0 efieotive 1 to o 1000. MYYBWI die'ihmfl amine nott egfsggive 1 not 1 to 5,000.- not 1 to 5,000-. not 1 to 5,000.

The functional character of the hydroxyl group in the butyl radical of the N-myristyl compounds of the present invention is demonstrated by the results obtained in the following tests:

Table IV Compound Interdigitale T. rubrum chloride. 10,000. 10,000

effective 1 to 1,000. 1, not 1 to 5,000.. not 1 to 5,000 efiect-ive 1 to eflective 1 to not efiective 1 effective 1 to effective 1 to not effective 1 All of the tests referred to in Tables I to IV above were conducted in accordance with the procedure given in Department of Agriculture Bulletin No. 198.

Compounds of the class of which the foregoing examples are typical may be used as bactericidal and fungicidal agents in various media as required for any particular use. .The compounds are stable and maybe stored for long periods of time at room temperatures and without deterioration.

Solutions containing 1 part by weight of N-myristyl-3- hydroxybutyl ammonium propionate dissolved in 5000 parts of water are bactericidal with respect to S. aureus and B. typhosus. In fact, every member of the class of compounds consisting of the N-myristyl-3-hydroxybutyl amines and their salts which has been tested has been found to be effective for use as bactericidal and fungicidal agents in relatively dilute solutions.

Bactericidal and fungicidal, or bacteriostatic, fungistatic compositions can be made by incorporating the N-myristyl-3 hydroxy-butylamines or their salts, described herein, in various materials as water and organic solvents such as hydrocarbons, alcohols, waxes, ointrnents, cutting oils, soaps, plastics, detergents, dispersions and used as such; for agricultural applications such as in seed treatments, control of scab and other diseases occurring on fruit or vegetation and control of diseases that occur on the turf grasses, as well as many industrial applications such as the treatment of textiles, leather, paper and in the control of slime. In soap, for example, around one part to one stitute a new class of compounds possessing unique and characteristic properties.

I claim:

1. N-myristyl amines and salts thereof wherein there is at least one S-hydroxybutyl radical attached to the amino group.

2. A hydro-halogen salt of an N-myristyl amine wherein there is at least one 3-hydroxybutyl radical attached to the amino group.

3. A compound having the formula (myristyl) 014E129 N-ClHBOH (butanol group) the composition indicated by the composition indicated by (myristyl) CuHza C4HaOH (butanol group) /N X R H wherein R is selected from the group consisting of hydrogen, alkyl and monohydroxy alkyl, X is an anion, and

7 8 the hydroxyl radical of the butanol group is attached to 1 References Cited in the file of this patent the carbon atom third removed from the nitrogen of the UNITED STATES PATENTS 7 7 7 1,836,048 Somerville Dec. 15, 1931 N-mYr!StY1-3hydroxybutylamme- 5 2,297,221 Huttenlocher Sept. 29, 1942 y g Y y p p p 2,541,088 Nikawitz Feb, 13, 1951 7- N-myns yl-3-hy r xy-2-m hyl p py ,5 7 s Jan, 1, 1952 8. N-myristyl-3-hydroxybutyl ammonium halide. 4 9. N-myristyl-3-hydroxybutyl ammonium chloride. OTHER REFERENCES 10. N-myristy1-3-hydroxybutyl ammonium propionate. Shelton et al.: J. A. C. 8., vol. 68, 753-759 (1946). 

1. N-MYRISTYL AMINES AND SALTS THEREOF WHEREIN THERE IS AT LEAST ONE 3-HYDROXYBUTYL RADICAL ATTACHED TO THE AMINO GROUP. 